Plasticizing agents



imam. 21, 1950 2 497 920 V UNITED STATES PATENT OFFICE 2,497,920 PLASTICIZING AGENTS Willard H. Woodstock, Flossmoor, 111., alimor to Victor Chemical Works, a corporation of Illinob No Drawing. Application January 26, 1046,

Serial No. 643,772

8 Claims. (Cl. 105-177) l 2 This invention relates to alkyl alkenylphoswhere R is an alkyl group oi 4 to 8 carbon atoms. phonates, and more particularly to plasticizin R1 is hydrogen or alkyl. and R1 represents an compositions including dialkyl alkenylphosphoalky] or My] group. and the t t number of z'ggg zz fi group contains fmm four bon atoms in the compound is more than 14 and 5 The method of producing such compositions is agf g than 24 are satisfactory for use as was disclosed in my copending application, Serial No. 590,956, filed April 28, 1945, now U. s. Patent No. v The following table shows'some f the P 2,471,472. This application is a continuation in ties of some typi al compounds Within e part thereof. 1 mula:

Compound & oint' ggg l t a so lfi ty,

gJsq. om. gJliter Di-n-butyl styrylhosphonate. 200-5 (3 mm).... Glassy at 76 0. 100 0. 0108 Did-amyl styryl-p osphonate 200-12 (4 mm.) Glassy at -73 0.005 0.0l6l. Dioctyl styr -phosphonate. 238-40 (3 mm.)-- Glassy at -79 0. 0011 0.0109 Dioctyl i-butenyl-phosphonatt... 180-5 (3 mm.). Semi-solid at 80- 0. 032 0. 0150 Di-i-emyl i-octenyl phosphonala 168-73 (4 mm.). Very viscous at -80... 0.037 0.0140 Dioctyl i-octenyl-phosphonate 214 (4 mm.). Semi-solid at -80 0.0078 0. 0345 While the method is described in more detail in The above phosphonates are compatible with the said application, the esters are produced by ethyl cellulose, nitrocellulose, cellulose acetate. first forming an addition product of an olefine and vinyl chloride polymer resins, and are exand PCl-s, and reacting that compound with P205 cellent plasticizers for these resins in amounts to produce a phosphorus oxydichloride which s from 20% to 40% by weight of the plasticized then esterlfled. For example, dioctyl styryl-lproduct, except that the octyl esters are not comphosphonate ester may be prepared by first formpatible with cellulose acetate. ing styryl-l-phosphorus oxydichloride and reacthe e m 8- v y c o P as e ing it with an excess of anhydrous 2-ethylhexin the claims is intended to mean a resin containanol (octyl alcohol) at a temperature below C. 30 ing at least 80% vinyl chloride and from zero to Dloctyl styrylphosphonate has a very low evap- 20% vinyl acetate. oration rate of 0.0011 gram per sq. cm. of surface The followin ab Shows plasticizin tests in 100 hours at 100 C. It may be assumed that made with the above-named resins prepared by 0.10 gram is as high an evaporation as is permismixing the resins with the plasticizers specified, sible for plasticizing use of such compounds. 3 dissolving them in a suitable solvent and casting Alkyl alkenylphosphonates having the following them into a thin coating or film and evaporatin formula ofi the solvent. The films thus produced were R0 R1 strong, clear, and flexible. They showed no tendency toward separation of the plastlcizer, and except for the nitrocellulose containing films, all no 3 ii a, showed improved flame resistance.

Resin Plasticizor 5%}:32 Solvent qgg, at

C0 lymer of 95% vinyl Dioctylstyryl-phosphonate. 26 Methyl ethyl ketone.. 1% of plestlcizer. c oride, 5% vinyl ace- Dioctylioctenyl phosphon 26 ...-.do 8% 0! plzsticlzer. tate. Dibutyl styryl-phosphonate 13% of pasticizer. Dioctyl i-butenyl-phosphonate 39% of p astlcizer. Dibutyl i-butenyl-phosphonete. of p. asticizer. Dibutyl i-octenyl-phosphonate 26 ...d0 59% of asticizer. Nitrocellulose Dioctylstyryl-phosphonate 26 Methyl ethyl ketone. 1% ol pYuticiur.

But lacetete, Ethyl elco ol, 'Ioluol. Dibutyl styryl-phosphonate 26 d esticlrer. Dloctyl i-octenyl-phosphonate .astlcizer. Dibutyl i-butenyl-phosphonate asticlzer Dioctyl i-butenyl-phosphonate. astlcizer Dibutyl iocteuyl-phosphonata- Ethyl cellulose Dloctylstyryl-phosphonate 167 oi- 18 a of p est clzer. 237 of p m irer.

D'octyl i-0ctenyl-phospl1onete..... Dbutyl styryl-phosphonete B- butyl i-octcuyl-phosphonatebutyl l-buteu yl-phosphonatep esti cizer octyl ibutenyl-phosphonate. oi izar Cellulose acetate D butyl styryl-phosphonete 17% of plast:.clzer Dibutyl i-butenyl-phosphonate- 43 a of Dibutyl i-octenyl-phosphonata... 43 do 51% 0| plasticizer Octyl esters Not compatible 1 Mixed solvent: 207 meth l ethyl ketone, 207 butyl acetate, 30% ethyl alcohol, and 307 toluol (by weight). a Mixed 10mm: toluol and 20% ethyl alcoiiol (by weight).

While some of the volatility figures given in the above table appear high, it does not mean that the particular ester is unsatisfactory as a plasticizer. For thick coatings and cast plastic articles-the volatility of the plasticizer is of considerably less importance than it is in the thin film. Furthermore the volatility test is intended as a highly accelerated aging indication, and at normal temperatures the plasticizing esters shown above show little or no tendency to vaporize and are highly satisfactory in most commercial plastic applications.

The following table shows additional tests upon certain of the phosphonates:

sisting of alkyl and aryl groups, the total number of carbon atoms in the compound being more than 14 and not more than 24.

2. A material as set forth in claim 1 containing 60 to 80% by weight of nitrocellulose.

3. A material as set forth in claim 1 containing 60 to 80% by weight of ethyl cellulose.

4. A material as set forth in claim 1 containing 60 to 80% by weight of a vinyl chloride polymer.

5. A nitrocellulose composition containing 20 to 40% by weight of dioctyl styrylphosphonate.

6. A material of the class consisting of a vinyl chloride polymer containing from 80 to 100% vinyl chloride and up to 20% vinyl acetate, ni-

Emmi pertliglg l 1 11 111 1 Heat Fl Percent Percent Stability Sweatby Wt. by Wt. w Hr at 2?" out 0. w 0. 40 0. t-f .9}? 9% C Dloctyl styrylvinyl chloride 70 45 70 125 0. 1 0. 9 6. 7 3 20. 0 No phosphonate. polymer. 65 60 110 170 0. 2 0. 4 12.0 3 32. 0 No 145 220 0. 4 0. 5 l6. 5 3 42. 0 N0 33. 5 66 5 55 155 0. 2 0. 6 10. 2 3 E. 0 No Dioctyl i-butenyl- 30 do 70 65 175 9. 0 1. 5 l5. 5 5 42. 0 No phosphonate. 35 65 95 220 7. 7 l. 8 2X). 6 4 -53. 0 No 40 60 140 205 300 8.1 1. 7 26. 3 4 -62. 0 No 28. 5 71 5 58 100 167 8. 3 l. 6 l4. 0 5 38. 0 N0 Dioctyl i-octenyl- 30 .dO 70 30 60 115 2. 3 0. 1 16. 7 4 36. 0 No phosphonate. 35 65 60 95 1. 6 0. l 22. 4 4 43. 0 No 40 60 100 155 235 1. 5 0. 1 28. 7 4 53. 0 No 35. 5 64. 5 63 100 l. 6 0. 1 22. 6 4 44. 0 No Test procedures are described in 1nd. Egg. Chem. 35, p. 896 (i943 1 vinyl chloride poiymer-Copoiyrner 95 The phosphonate esters disclosed herein are disclosed and claimed in my copending application Serial No. 780,591, filed October 1'7, 1947, which is a continuation-in-part of the present application.

The foregoing detailed description has been given for clearness of understanding only, and no unnecessary limitations should be understood therefrom.

What I claim as new and desire to secure by Letters Patent is:

1. A plasticized material containing 80 to 60% by weight of a member of the class consisting of a vinyl chloride polymer containing from 80 to 100% vinyl chloride and up to 20% vinyl acetate, nitrocellulose, and ethyl cellulose, and approximately 20 to 40% of a compatible phosphonate ester having the formula:

"where R is an alkyl group of 4 to 8 carbon atoms, a is a member of the class consisting of hydrogen and alkyl groups, R: is a member of the class cona vinyl chloride and 5% vinyl acetate.

trocellulose, and ethyl cellulose, and 20 to 40% by weight of dioctyl styrylphosphonate.

7. A material of the class consisting of a vinyl chloride polymer containing from 80 to 100% vinyl chloride and up to 20% vinyl acetate, nitrocellulose, and ethyl cellulose, and 20 to 40% by weight of dioctyl iso-octenylphosphonate.

8. A material consisting of a vinyl chloride polymer containing from 80 to 100% vinyl chloride and up to 20% vinyl acetate, and 20 to 40% by weight of dioctyl styrylphosphonate.

WILLARD H. WOODSTOCK.

REFERENCES CITED The following references are of record in the tile of this P tent:

UNITED STATES PATENTS Number Name Date 2,365,466 Hamilton Dec. 19, 1944 2,385,879 Patton Oct. 2. 1945 OTHER REFERENCES Chemical Industries, vol. 55 (October 1944), pages 580 and 581. 

1. A PLASTICIZED MATERIAL CONTAINING 80 TO 60% BY WEIGHT OF A MEMBER OF THE CLASS CONSISTING OF A VINYL CHLORIDE POLYMER CONTAINING FROM 80 TO 100% VINYL CHLORIDE AND UP TO 20% VINYL ACETATE, NITROCELLULOSE, AND ETHYL CELLULOSE, AND APPROXIMATELY 20 TO 40% OF A COMPATIBLE PHOSPHONATE ESTER HAVING THE FORMULA: 